CH2105 – Energy Changes in Molecules and Atoms – Thermodynamics

-the science of transformations of energy

-a macroscopic science; -the study of bulk properties
-things that can be measures in a laboratory (i.e. volume, pressure)
-no need to know about molecules or molecular theories

With thermodynamics several things can be found;

-the position of equilibrium
-most likely reaction/products formed
-determination and interrelationship of properties
-assessment of reactivity vs. stability – spontaneity

Thermodynamics can’t determine how fast a reaction will go, i.e. the kinetics of a reaction.

Thermodynamics can be used to optimise conditions in equilibria reactions, calculate energy

changes for reactions too difficult to perform (by using Hess’s law), predict the most stable form of a
substance or product, predict the variation of the equilibrium constant with varying pressure or
temperature and investigate the properties of solutions.

The Basic Concepts of Thermodynamics

Universe= System + Surroundings

The part of the universe we are Everything else in contact
interested in; -solutions in a beaker with the system which can
-chemical reactor influence its state.

In an open system there is an exchange of energy and matter between the system and its
surroundings.
In a closed system there is only energy exchange between the system and surroundings.
In an isolated system there is no exchange of matter or energy between the system and
surroundings (note that these are never seen in reality as there is always a slight opening in the
system to allow for the addition of chemicals/gauging of temperature etc. which allows for some
exchange of at least energy).

Thermodynamic Variables and Denoting Changes

Heat Q A large change is denoted by ∆, a small change by δ and infinitesimal

Work W changes are denoted by d.
Internal Energy U
Pressure P
Temperature T
Volume V
Work, Energy and Stability
Using the example of pushing a boulder up a hill;

height Potential
Stable energy

h2 3 mgh2

Unstable

mgh1
h1 2
Force, F
Metastable
1

Stable

From 1->2 work must be done;

Work=Force x Distance
Work= f(d1-d2) in Joules (J)

To determine the energy;

Energy=Gravitational force x Height
Energy= mg(h1-0) in Joules (J)

Low energy therefore leads to thermodynamic stability which in turn leads to equilibrium. A system
always moves towards minimum energy and equilibrium.

State Function
A state function is dependant only on the initial and final states of the system and not the path taken
to reach that state, energy is therefore a state function, however work is not.

The First Law of Thermodynamics

The first law of thermodynamics is based upon the principle of the conservation of energy; ‘energy
may be neither created nor destroyed but converts from one form to another’ and is stated as ‘the
total energy of an isolated system is constant. Or as an equation;

Internal Change=Heat + Work

All different forms of energy have an associated work that may affect the energy of a system;

∆U=∆Q + ∆W for a change in internal energy

In order to do anything useful with this equation ∆Q and ∆W must first be related with physical
phenomena taking place in the surroundings. For this work is considered not in terms of the work
done on a system but in terms of the work done by the system;

Work a system does=-(Work done on the system)

Sign Convention
A change in heat or work that increases the internal energy of the system is defined as a positive
change.
Heat (∆Q) + IN (absorbed by system)
- OUT (absorbed by surroundings)
Work (∆W) + DONE ON SYSTEM
- DONE BY SYSTEM

In general the work done on a system can be expressed in the form;

dW=-Fdz where F is a generalised force

and z is a generalised displacement

Free expansion occurs when Pext=0, since dW=-PextdV ⟹ dW=0

In a vacuum there is no opposing force to push against so no useful work is done.

Reversible expansion occurs when Pext is variable from P1 (Pint) to P2 (Pext) and Pext is allowed to
change in small increments so that it is always slightly lower than Pint the expansion will proceed in
tiny steps. The expansion is reversible as if at any time Pext is increased by an infinitesimal amount to
be just greater than Pint the gas will compress slightly and the system could be returned to its
original state by a series of reversible compressions.
The system is at all times in equilibrium.

If the gas is, at all times, ideal then PV=nRT

−dW = PdV P = Pint = Pext

nRT
−dW = dV
V

W2 V2
1 dx
− dW = nRT dV [note, = lnx]
V x
W1 V1

V2
−∆W = nRTln V1
and at constant temperature P1V1=P2V2
P1
Therefore; −∆W = nRTln P2
Maximum work is obtained, under isothermal, reversible conditions.
Enthalpy – H
The first law states that; ∆U=∆Q+∆W, which can be simplified to ∆U=∆Q - PdV
To calculate ∆W pressure must be known as a function of volume, however since not all systems can
be simplified as ideal, PV=nRT cannot always be used. Instead the integration is simplified by the
study of the system at either constant volume or constant temperature.

At a constant volume; dV=0 and therefore ∆U=∆Qv

constant pressure; -∆W=P∆V and therefore ∆U=∆Qp-P∆V

Since most reactions proceed at a constant pressure (i.e. no gas is evolved) it is convenient to define
a new energy function, enthalpy – H.

H=U+PV
∆H=∆U+P∆V=∆Qp

The enthalpy is obtained by measuring the heat absorbed at a constant pressure.

For a reaction at constant pressure and temperature which involves a change in ∆n, the number of
moles of gas;

∆H=∆U+∆nRT

Measuring ∆H
Enthalpy cannot be measured directly, and since at constant pressure ∆H=∆Qp, the heat of a system
must be measureable.
Temperature can be measuring using a thermometer, temperature is related to heat by;

∆Q∝∆T
∆Q=C∆T where C is the heat capacity
∆H=∆Qp=Cp∆T
Experimental Determination of ∆H
Calorimetry
-a simple experimental arrangement of endothermic and exothermic reactions

Heater
System

Thermometer Stirrer

-the system is placed in the water bath and the reaction initiated
-Temperature is monitored as a function of time
-The heater supplies electrical work to mimic the temperature change in the system

∆Welec=vIT, where v=volume

I=current
t=time

Adiabatic Bomb Calorimeter

-used for combustion
-sample ignited under a high pressure oxygen, ≈30atm
-the bomb is a sealed, constant volume container, this is immersed in a water bath
-the whole calorimeter is heated to a constant temperature
-the temperature change in the calorimeter water bath is monitored
-calorimeter heated to the same temperature to ensure no loss of heat to the surroundings (thus
adiabatic)
-the heat capacity of the whole calorimeter must be known

Heater

O2 Bomb

Stirrer

Thermometer
Using Heat Capacities
There are two potential scenarios in which heat capacity is used;
a) If Cp is independent of temperature;
-a good approximation for many liquids

dH
∆H=Cp∆T ∴ Cp= dT

Rearranged and integrated this gives;

H2-H1=Cp(T2-T1)

We can therefore determine the enthalpy change for a substance with a known heat capacity under
a given temperature change.

b) If Cp is a function of temperature
-true for gases and solids
c
Heat capacities can be expressed as Cp = a + bT + T 2

Integrated and simplified this gives;

b 2 1 1
∆H = a T2 − T1 + T2 − T12 − c( − )
2 T2 T1
The Significance of Enthalpy
Chemical reactions almost always involve a change in heat.
Exothermic (-∆H) – liberating heat or Endothermic (+∆H) – absorbing heat

Enthalpy is the heat content of a system at a constant pressure where the only work done is
pressure.volume work. Therefore, if H is known for every substance, ∆H can be calculated
(∆H=∆Hproducts-∆Hreactants) for any reaction without ever having to do an experiment. It is not possible
to measure absolute enthalpy, only changes from one state to another, and thus a reference state is
defined from which all other states are measured.

Standard States
The standard state of a substance is defined as being its most usual form at 1 bar pressure and the
specified temperature, usually 25oC (298.15K)

The absolute enthalpy of the elements in their standard states is 0

o
I.e H298 [C(s)]=0

Standard Enthalpy Changes

∆Ho is the change in enthalpy for a process in which the initial and final substances are in their
standard states.

Enthalpy of Formation
∆Hfo [x] is the enthalpy of formation of a substance from its elements in their standard states.

Enthalpy of Vaporisation
∆Hvo [x] is the enthalpy change per mole when a pure liquid vaporises to a gas at 1 bar pressure.

Enthalpy of Combustion
∆Hco [x] is the standard reaction enthalpy for the oxidation of an organic substance to CO2 and H2O.
Hess’s Law and Reaction Enthalpies
-energy, or enthalpy is conserved
-enthalpy is a state function and depends only on the initial and final states

∆H for any chemical reaction is independent of the reaction path, it is the same whether the reaction
is carried out in a single, or several stages.

For any reaction;

o o o
∆Hreaction = Σ∆Hformation products − Σ∆Hformation reactants

∆Hf is not known for many compounds however, in some cases it must be calculated using Hess’s
Law.

Enthalpy of Solution
∆Hso [x] is the standard enthalpy change when a substance is dissolved in a specific amount of
solvent.
It is effectively the heat of formation of ions in aqueous solution; many biochemical and
physiochemical reactions involve ions in solution.
The enthalpy of formation of an ionic compound in solution can be regarded as the sum of
enthalpies of formation of the constituent ions. It can be analysed into several steps, known as a
Born-Haber Cycle.

Born-Haber Cycles
The steps can be drawn into a cycle or complete process. Since enthalpy is a state function the
overall enthalpy change around the cycle must equal zero.
The Second Law of Thermodynamics
There are many naturally occurring spontaneous processes, i.e. gas expanding into a vacuum, that
usually do not go in the reverse direction. The influence of enthalpy is shown through heat loss in
spontaneous processes, however some spontaneous processes absorb heat, something other than
enthalpy contributes.
This other influence is disorder, if heat were to be the only influence it would be expected for all
molecules to be ordered which is an impossibility.

The second law is therefore stated as;

Spontaneous processes occur in the direction of increasing disorder or chaos.

To quantify disorder the term entropy (S) is used;

-as with enthalpy there is no direct method for measuring entropy
-entropy is a state function, and in an isolated system it can only ever increase or remain the same

Entropy is linked to the Boltzmann equation;

S=KBlnΩ where KB=Boltzmann Constant=1.38x1023J K-1

and Ω=the number of distinguishable ways of arranging the individual molecules over the set
of position available to them.

 S increases for solid→liquid→gas

 S increases for a solid dissolving in water
 S increases with chemical complexity
 S decreases for a gas dissolving in a liquid
 S decreases with increasing bond strength
 S increases with temperature (due to the population of energy levels)

The Third Law of Thermodynamics – Absolute Entropies

The entropy of a perfectly pure crystalline substance is zero at absolute zero, 0K

I.e. when Ω=1, S=KBlnΩ=0

In practise most substances have ‘residual’ entropy and are not truly perfect.
The energy associated with entropy is J K-1, and for a heat only energy change;

∆Q=T∆S

∆S for Reversible and Irreversible Reactions

For a reversible process ∆S=0 – i.e. in an isolated system entropy remains constant.
For an irreversible process ∆S>0 – i.e. in an isolated system entropy increases.

∆S can never be negative, although ∆Ssys and ∆Ssurr may be positive or negative, the net change must
always be greater than or equal to zero entropy can never decrease.
Entropy Changes upon Heating
To calculate the entropy change in a system raised from T1 to T2;

T2
∆S=Cp.ln
T1

Gibbs Free Energy

G=H-TS
∆G=∆H-T∆S

Gibbs energy is the available energy free within a system (in J mol-1)
It determines;

 Whether a reaction will proceed or not

 Which direction a reaction occurs in
 Whether a material is stable

It is temperature and pressure dependant.

The variation of G with temperature is given by the integrated Gibbs-Helmholtz equation;

∆G2 ∆G1 1 1
− = ∆H −
T2 T1 T2 T1

The variation of G with pressure is given by;

P2
∆G = nRTln
P1

If P1=1 bar and G1=Go (Standard Gibbs Free Energy) then this simplifies as;

G=Go+nRT ln(P)

Using this equation it is possible to calculate G at any pressure and constant temperature.
Chemical Equilibrium
Reactions will move towards dynamic equilibrium.
At equilibrium reactants and products are present but have no tendency to undergo net change.
Thermodynamics can predict the equilibrium composition at different pressures and temperatures,
industrially this is used to maximise product yields.

At equilibrium the system is dynamic and so;

aA+bB⇋cC+dD

There is a continual change in material.

If we observe the Free Energy of the system with change in composition;

Gtotal=naGo(A)+ nbGo(B)+ ncGo(C)+ ndGo(D)

Where n=the number of moles and Go=the Free Energy of 1 mole. Therefore;

∆Greaction=ΣG(products)-ΣG(reactants)

Gtotal Gtotal

aGo(A)+ bGo(B)

cGo(C)+ dGo(D)
∆Gr=-ve ∆Gr=+ve
Equilibrium

Spontaneous ∆Gr=0 Spontaneous

forward reaction backward reaction

pure reactants Chemical Composition pure products

For gaseous equilibria;

PCc PDd
∆Greaction = ∆Go + nRT ln
PAa PBb
P cC P dD −∆G o
Kp = where Kp= exp
P aA P bB RT

The Effect of Temperature on Equilibrium

To calculate k at any given value of T the Van’t Hoff equation is used;

∆H o ∆S o
lnk = − +
RT R

The Effect of Pressure on Equilibrium

The equilibrium constant is given by ∆Go=-RT ln(kp) where ∆G0 is defined for reactants and products
at 1 bar.
∆Go and Kp do NOT change with pressure, however the amounts of gases at equilibrium does
change, using an example of N2O4⇋ 2NO2;
 N2O4 ⇋ 2NO2
Initial 1 0 Ptotal=1+ α
At Equilibrium 1-α 2α

2αP 1−α P
PNO 2 = and PN 2 O 4 =
(1 + α) (1 + α)

2αP 2
2
P NO2 (1 + α) 4α2
Kp = = = P
PN2 O4 (1 − α)P 1 − α2
(1 + α)

Kp
α=
Kp + 4P
and so; α depends on P, and given P it is possible to calculate the amount
of reactant and product at equilibrium at the pressure P.